2-alpha-carbonylated 8, 13-dimethyl polyhydrophenanthrene compounds and preparation thereof



United States Patent 2-a-CARBONYLATED 8,13-D1METHYL PoLYHY- DROPHENANTHRENE COMPOUNDS AND PREPARATION THEREOF Nicholas Thomas F arinacci, New York, NQY. I

i No Drawing. Application May 10, 1954 Serial No. 428,852

25 Claims. (Cl. 260-4685) This application is a continuation in part of my copending application Serial No. 198,895, filed December 2, 1950, and including certain pertinent disclosures herein, of copending applications Serial Numbers 198,893-4-2, said disclosures being filed on December 2, 1950, and pertinent disclosures in copending applications, Serial Numbers 416,433-4, filed March 15, 1954, and 610,623-4, filed September 18, 1956. I

This invention relates to new compositions of matter, the 2-oxygenated substituent-8,l 3-dimethyl polyhydrophe- .nanthrene-8-tertiary carbinols of the nuclearly saturated. monounsaturated and 'arornatized abietyl and d-pimaryl group of the phenanthrene series of compounds, and prep- .aration thereof.

This invention particularly relates to new compositions :such as the aceto, carboxy-ester and side chain halogen- :ated-polyhydrophenanthrene tertiary carbinols of the structure from the group consisting of hydrogen, alkyl and-'aryl radicals), --CHOHCH CHOHCH OH, and Cl-lpCH t, and preparation thereof. Y 1 More particularly the invention relates to new com pounds, the 2-aceto polyhydrophenanthrene-8-tertiary carbinols of the structure 2,830,075 Patented Apr. 8, 1958 are therapeutics themselves, useful especially for the.

treatment of disorders related with deficiencies of the seminal organs, testicular and pituitary glands, For ex ample, as described for the invention in copending applications (Serial Nos. 198,892 and 441,646) the novel products, herein, such as the 2-aceto-8-13-dimethyl nuclearly halogenated polyhydrophenanthrene-S-tertiary diphenyl carbinols or the corresponding 2-isopropyl carbinol halides of applications Serial Nos. 198,894 and 416,434, each is described as utilized for the preparation of such as the corresponding 7-ketoA(8,l4) (1,2)-2-aceto13 methyl polyhydrophenanthrene which latter is found to have androgenic properties and which also may be utilized further as a synthetic intermediate for such as the preparation of the natural cyclopentanopolyhydrophenanthrene hormones. a

An effect of this invention is the production of said halogenated aceto-tertiary carbinols by subjecting the ring-C unsaturated aceto polyhydrophenanthrene tertiary carbinols to the action of halogens or halogen hydrides in suitable solvents such as acetic acid, chloroform, carbon tetrachloride, ether-alcohol mixtures and the like, such methods 'being disclosed in said copending applications Serial Numbers 198,893-4-5-2 and 416,433-4, and as applicable generally for the preparation of halogenated-2 substituted polyhydrophenanthrene tertiary carbinols such as starting materials utilized herein, said preparation for starting materials for this case as described therein and the material prepared in accordance with description in this case and used in the preparation of other materials which descriptions, as set forth in said applications, are hereby incorporated, herein.

Another object is the subjecting of the corresponding nuclearly saturated halogenated dihydrolevopimaryl tertiary diphenyl carbinols derivable from the A(6,7) and A(7,8) derivatives, to the action of suitable oxidizing agents at temperatures below 60 C. whereby while the nucleus is protected by halogens from oxidation, the side chain isopropyl group is converted to an aceto group.

Still another object of this invention is the transformation of the products of oxidation, the halogenated aceto polyhydrophenanthrene tertiary carbinols to such as said aceto carbinols such as the structure I, wherein the double bond has been restored in the ring system by splitting ofi hydrogen halide or halogen. This is achieved not only by those reagents mentioned in the examples, as by treatment with pyridine bases or with zinc dust in acetic acid, respectively, but also other reagents may be used such as treatment with alkaline agents or the like, such as alkali iodides in alcohol and in accordance with other methods described for instance by Houben Die Methoden der Organischen Chemie 2d edition, vol. 2, pp. 744-746 U9 2)- Said starting materials, such as the nuclearly monoun saturated dihydrolevopimaryl tertiary carbinols and the corresponding halogenated tertiary carbinols such as coro respond to the general formula C H Omt and a structural formula such as wherein Ph designates phenyl and at least one of the m and t groups being halogen'and the other a member of the group halogen and hydrogen include certain derivatives of the A(6,7) dihydrolevopimaryl tertiary carbinols such as the monochloride of Example 3, herein, corresponding to halogen derivatives of the A(2,3)-8,13-di methyl polyhydrophenanthrene-S-tertiary carbinols having --CH(CH or (-COCH in the 2-position thereof. Said derivatives may be treated as by dehydrohalogenation, set forth herein, to provide the corresponding 2,3 unsaturated derivatives; wherein as for the 1,2 unsaturated derivatives the double bond is adjacent to the 2-isopropyl or 2-aceto group.

In accordance with said methods as are described herein and description'of preparations of starting materials as in the applications Serial Numbers 198,8934-5-2 and 416,433-4 based thereon, suitable starting materials such as are illustrated in examples herein are noted to be summarized as in the Formulas IV and V above, wherein R R s, m, t and 1 have the meaning set forth above and 11 may be t 3) 2), 2) 3) and (CHOHCH OH) or (CHpC H t) and the like and said starting materials may be utilized by such means as are illustrated herein, for the preparation of corresponding 2-oxygenated substituent polyhydrophenanthrene tertiary v carbinols selected from the group designated by Formulations Wand V. I V

The new aceto-carbinols obtained according to this invention preferably are prepared by treating such as the corresponding nuclearly unsaturated dihydrolevopimaryl diphenyl carbinols to saturate the double bond, for example, by adding on halogen or halogen hydride, and subsequently oxidizing the halogenated carbinol preferablywith amixture of an oxidizing chromiumcornpound such as hexavalent chromium oxide, a bichroma'te, chromate or chromyl compound and the like and preferably in admix ture with an orthophosphate producing compound such as orthophosphoric acid and the like at temperatures below C. The intermediate halogenated aceto polyhydrophenanthrene diphenyl carbinols may be treated, for example, the dibromicle or dichloride, with powdered zinc in acetic acid or the monochloride with pyridine at temperatures below C. to obtain the aceto polyhydrophenanthrene carbinol I. In like manner the halogenated d-pimaryl tertiary carbinols may be converted to corresponding Z-carboxy-R or 2-aceto derivatives.

I have found that it is desirable to control the temperatures during oxidation and dehalogenation to below 70 C., preferably below 60 C. to avoid excessive production of by-pro'duct acids and dehydrated products.

Although a preferred scheme for the oxidation process of this invention comprises the reaction of such as the suitably protected halogenated dihydrolevopimaryl,terti= ary carbinolswhich have the Formula I'll in glacial acetic acid with a mixture of an oxidizing chromium compound such as CrO and the like, and an at least sufficientamount of an orthophosphate producing compoundsuchas H 'PO to remove all the trivalent chromium-ion formed during reactionas an insoluble solid phase at a temperature be yl carbinol. This product yielded 12 grams of the Z-aceto tween 30 and 60 (3., it will be immediately apparent to one skilled in the art that the proportions and concentrations of the reactants, as well as the temperature and period of reaction may be varied within wide limits and the acetic acid medium may be replaced by a tertiary alcohol or other inert solvents such as carbon tetrachloride and acetone. carried out over a fairly wide range of temperature varying from about 5 C. to as high as 60 C. At the higher temperatures the oxidation is complete within a few minutes while at 5 C. the reaction may. take several hours. The oxidizing chromium compound may be CrO a bichromate, chromate or chromyl compound while the orthophosphate ion producing compound maybe one of the orthophosphoric type of compounds which include the ortho, meta and pyrophosphoric acid and their acid salts such as may revert to orthophosphates on hydration.

The following examples serve to illustrate this invention, withoua however, limiting the invention to them.

Example 1 i To 210 grams of 7,8-dibromdihydro'levopimaryl terti ary diphenyl carbinol dissolved in 3 liters of glacial acetic acid a mixture of 50 grams of ,CrO and 200 grams of aqueous orthophosphoric acid are added dropwise with stirring while maintaining the temperature between 30 and 50 C. The reaction is completed by stirring for minutes after addition of the CrO and the chromic phosphate precipitate is removed by filtration and washed with ether to recover occluded organic products. The filtrate is watered out to 10 liters with water and freed of acetic and phosphoric acids by filtration. The combined organic productsare recovered in ether and dried by distillation under vacuo. nanthrene diphenyl carbinol is recovered in the residue by washing the residue with petroleum ether, B. P. 30 to 60 C. It is purified further by washingthe ether solution of the residue with 5% aqueous alkali (NaOH) to remove by-product acids. The recovery of aceto dibrompolyhydrophenanthrene diphenyl carbinol was 200 grams, a yield which analyzed 26.0% bromine, refractive index 1.5881.

The sample of 195 grams of aceto-dibrornpolyhydrophenanthrene diphenylcarbinol is dissolved in 2 liters of glacial acetic acid andtreated portionwise at 50 with 300 gms. of zinc dust over a period of 2 hours. The mixture is then warmed to 90 C., for 15 minutes and filtered and the solutionn is watered out to 6 liters volume. The organic residue is washed free of salts recovered in ether solution and dried in vacuo. By exhaustive petroleum ether extraction of the residue 130 gms. yield of crude aceto polyhydrophenanthrene diphenyl carbinol I was obtained which analyzed 1.3% bromine, 83.2% C, 8.5% H

Example 2 225 grams of 7,8-dichlordihydrolevopimaryl tertiary diphenyl carbinol are oxidized as in Example 1, to provide 215 grams of 7-aceto-7,S-dichlordihydrolevopimaryl tertiary diphenyl carbinol,.13.4% chlorine. This product yielded gms. of crude aceto polyhydrophenanthrene diphenyl carbinol I when dehalogenated as inExample 1.

Example 3 19 grams of 7-monochlordihydrolevopimaryl tertiary diphenyl carbinol, prepared from dihydrolevopimaryl tertiary diphenyl carbinol by addition of HCl to the double bond, were oxidized by a mixture of 10 grams of CrO and 38 grams of 85% aqueous orthophosphoric acid as in Example 1. Sixteen grams of a product was recovered as in Example 1, which had 7.3% Cl corresponding to the 7-aceto-monochlordihydrolevopimaryl tertiary diphenpolyhydrophenanthrene tertiary diphenyl carbinol I when dehydrohalogenated with hot pyridine on the steam bath.

For example, the oxidation may be.

The aceto dibrompolyhydrophet luEt mpl -t I d-pimaryl tertiary diphenyl carbinol as disclosed in Example 4 of copending application Serial No; 198,892 (refiled as 441,646), is utilized herein to prepare the corresponding carboxy-phenyl derivative. 15grarns of 8,14- dibrom-7-hydroxy-ethyl d-pimarylfmethyl-ester istreated with 30 gramslof P in 200cc. glacial acetic acid and the dibrom-d-pimaryl methyl-ester so produced is treated with a mixture of 4 grams of -CrO and 50 grams of 85% aqueous H PO at 50 C. and the product 7-carboxy-8,14- dibrom-d-pimaryl ester is treatedwith grams powdered zinc to yield the corresponding A( 8, 14) derivative'which is treated with PhMgBrjin accordance with the process as set forth: in appliciationsSerial 'No. 198,393 (refiled as Ser. No. 416,433) to provide the 7-carboxy-A(8,14) d-pimaryl tertiary diphe'nyl carbinol which is esterified with phenol and treated with HCl in ether-alcohol to provide Z-carboxy-phe'nyl-ll-chloro-2,8,13-trimethyl polyhydropheneinthrene-S-tertiary' diphenyl carbinol. Alternatively, grams of d-pimaryl tertiary diphenyl carbinol treated with dilute (5%) KMnO ina 50-50 mixture of aqueous acetone to yieldthe corresponding 7-glycol which may be brominated to yield the 14,8-dibrom-7-glycol-dpimaryl tertiary diphenyl carbinol whichis treated with 4 grams of CrO and 50 grams 85% aqueousH PO at 60 C. thus providing the 2-carboxy-11,-l-dibrom-2,8,13-trimethyl polyhydrophenanthrene-S-tertiary diphenyl carbi- 1101 which may be .esterified with alkyl alcohols or phenols to produce the'corresponding -2-carboxy-R-d'erivatives, thereof. In like manner the corresponding tertiary alkyl carbinols, for example, the tertiary dimethyl-Z-carb Xy-R carbinols may be prepared. Said method comprises the following: 10 grams of 7-carboxy methyl diphenyl tertiary carbinol prepared from nuclearly saturated dibrom-d pimaryl methyl ester by oxidation of the side chain, dehalogenation, grignardization' and esterification having the structure COOCHI oon wherein Ph is phenyl, dissolved in 200 grams of glacial acetic acid is treated with 4 grams of bromine with stir ring for minutes, thereby providing the 11,1-dibrom-2- carboxy-methyl-2, 8,13,-trimethy1 polyhydrophenanthrene- 8-tertiary diphenyl carbinol.

Example5' f 10 grams of the 7-hydroxy-ethyl d-pimaryl tertiary diphenyl carbinol prepared asin Example 4, by omitting'ithe P 0 and bromination treatment is obtained by treating I Eicample 6 V v e 2 grams of dehydroabietyl tertiary diphenyl carbinol prepared as in copending application Ser. No. 416,433

and (198,893) is treated with 4 grams of CrO and 50 grams of HgPO; at 50 C. to yield' 1.5. grams of 2 aceto 10-keto-8,13-dimethyl polyhydrophenanthrene-8-diphenyl carbinol having the structure in which the C ring is aromatic.

'In the above examples such as the Z-hydroxy-ethyl and 2-carboxy tertiary carbinol derivative may be freed'from the 2-hydrocarbon substituted carbinols by extraction of the latter by petroleum ether or hexane.

The nomenclature and numbering are defined in this specification and claims for the phenanthrene series those found in Journal of the American Chemical Society 55, 3905(1933), and those for the abietic series conform with the systems in Journal American Chemical Society 60, 159(1938), and Fieser and Fieser Natural Products Related to Phenanthrene, chap. II, 3rd ed. (1949), Reinhold Publishing Co., New York, N. Y. i

The said abietyl and d-pimaryl group'of phenanthryl compounds is noted to comprise the abietic series which includes under the term abietylzabietic, neoabietic, dehydroabietic and levopimaric whose carbon skeleton and numbering is noted in Formulation 1, below to OH; "5 H O CH3 /-4\ 13 3 12 14 HaO b pp. 41 and 58, denotes the conjugated diene dimethyl tricyclic residue H10 1) having abietic series numbering and terms dihydrolevopimaryl denotes in general corresponding partially hydrogenated residues, thereof, wherein b has the meaning defined above'and' n'may be CH(CH COCH said hydrogenated residues having C ring structures and disclosed herein as 'preparable from such as'th e tertiary guano-rs c carbinols' ofaexarnple 3, herein, Tsu'chias the 7-monochlor; derivatives from which. by dehydrohalogenation as :dis closed herein, may provide the ..A(2 ,3) 8,13 dimethyl 2s isopropyl or 2-aceto polyhydrophenanthrenes-8rtertiary c'arbinols from which the corresponding 2,3 dihalides may be ,preparedaccordingtto the haloge'natedprocess disclosed as in copending applications Serial Numbers 416,434 (198,894)-198,895 and,198,892. The preparations for Starting materials for this (case are described in copending applications Serial, Numbers 416,433-4 and (198,893-4-5-2) which descriptions are hereby,incorporatedherein. 4 4 i Thematerials prepared in accordance with descriptions in thiscase are used in the preparation of other materials as set forthin copending cases Serial Numbers 416,433-4 (198,893-4-5-2) which descriptions asset forth in said cases is hereby incorporated, herein.

The foregoing may be summarized as follows;

The starting polyhydrophenanthrene compound may be represented by the'forrnula wherein n is selected from the group consisting of CH3 2, CII

and -CHOHCH OH.

This material is oxidized by means of oxidizing agents,

preferably a hexavalent chromium compound, preferably i wherein n is selected from the group consisting of -CO.CH and COOR.

In all the foregoing formulas b is selected from the group consisting of -COOR (wherein R is selected from the group consisting of hydrogen, alkyl and aryl radicals), and --COHR R (wherein R and R are each selected from the group consisting of the alkyl and aryl radicals), v is selected from the group consisting of =0 and =H w and u are each selected from the group consisting of hydrogen and one end of a double bond, s, t and p are each selected from the group consisting of hydrogen, halogen and one end of a double bond, m is selected from the group consisting of hydrogen, halogen, methyl and one end of a double bond, said ends of double bonds being in a position selected from the group consisting of the w and u, s and m, m and t, and t and p positions.

The group of inventions comprised in the copending applications as noted below relates to converting the readily available .pine resin acids to materials having androgenic activity, ,which materials may be further con verted to natural cyclopentano polyhydrophenanthrene typ f mo y a e escribed andiclairned in copending applications SerialNo. 610,623, Serial No. 610,624, Serial No. 428,852, Serial No" 610,625 and Serial No. 647,986. In this overall process an ester derivative of apine resin acid is converted to a tertiary carbinol by grignardization. I

In this connection there are included an improved method for/obtaining high yields of carbinol of the order of 95% 'of theory by operation at elevated temperatures with highboiling solvents, and also a novel method ofv recovery of the high yield ofv desired carbinol products in substantially pure form by degradation and removal of the unreacted acid'esters therefrom, and also a method for rearranging and dehydrating the tertiary carbinol product to corresponding tertiary diphenyl-methyl .com- 4 pounds. These novel features and intermediate compounds are described and claimed in copending application Serial No. 610,623, filed Sept. 18, 1956' as a continuation-in-part of Serial No. 416,433, filed March 15, 1954, as a continuation-in-part of application Serial No. 198,893 filed Dec. 2, 1950, both of the latter now abandoned.

The class of nuclearly monounsaturated tertiary carbinols obtained thereby are converted to corresponding saturated halides by halogenation or hydrohalo'genation which features and carbinol halide products are described and claimed in copending application Serial No. 610,624 filed Sept. 18, 1956, as a continuationfin-part of Serial No. 416,434 filed March 15, 1954, as a continuation-inpartof application Serial No. 198,894 filed Dec. 2, 1950, both of the latter now abandoned.

The resulting carbinol halides and the corresponding C-ring aromatized tertiary carbinols' (obtained as above from the corresponding aromatized pine resin acids) are subjected to selective oxidation which converts the 2-side chain of the polyhydrophenanthrene tertiary carbinol to an alpha carbonyl group, which features and carbinol products are described and claimed in the present application filed May 10, 1954, as a continuation-in-part of application Serial No. 198,895 filed Dec. 2, 1950, now abandoned. I

The carbinol in the material obtained by any of the above discussed methods is-rearranged and dehydrated to provide a tertiary diphenyl methyl compound, an (8,14) unsaturated double bond is formed by removal of elements of water from the rearranged carbinol and the resulting compounds are oxidized on the active methylene group therebyformed which is adjacent to the said tertiary diphenyl methyl group, to provide the corresponding alphaand lactones, andthese may be converted to the conespending above mentioned 7-keto polyhydrophenanthrene compounds by treatment with an acetylating agent as by treatment with phenyl acetosodium hydride reagent (or with methyl halide magnesium salts) which features and intermediate polyhydronapthalene compounds are described and claimedt'in copending application Serial No. 647,986, filed March 25, 1957, as a continuation-in-part of Serial No. 390,747 filed Nov. 6, 1953, as a continuation in-part of application 'Serial No, 260,231filed June 6, 1951, both of the latter now abandoned.

The above mentioned 7-keto polyhydrophenanthrenes assess-s wherein b is a tertiarily bound group suchas CO0R, -COHPh and -cH,oH, 'CH NH' 1 wherein R and Ph have the definition defined herein and (2) in terms of a polyhydrophenanthrene nomenclature and numbering, wherein the tricyclic numbering is as shown in the same carbon skeletons, as shown in the formula below, both of which are used herein, to conform with both as used in Fieser and Fieser, Natural Products Related to Phenanthrene, chap. 2, 3rd ed., ReinholdPubl. Co., N. Y., see pp. 41, 64 and 85, thereof, particularly.

I claim: 1. A process for the production of an 8,13-dimethyl polyhydrophenanthrene compound having as an 8-sub-,

stituent a tertiarily bonded radical selected from the group consisting of a tertiary-carbinol, a carboxyl, a carboalkoxy and a carboaryloxy radical and having as a 2-substituent an a-carbonylated aliphatic radical selected from the group consisting of -COCH and -COOH from a corresponding 8,13-dimethy1 polyhydrophenanthrene reactant compound having said tertiarily bonded 8-substituent and having as a 2-substituent a member of the group consisting of CH(CH CH=CH CHOHCH and -CHOHCH OH, the nucleus of which reactant compound is resistant to rupture by oxidation under the process conditions and the 13-angular methyl group and the said S-tertiarily bonded substituent are in trans relationship, which process comprises subjecting said reactant to the action of a hexavalent chromium compound under oxidizing conditions, whereby said compound having said Z-a-carbonylated substituent is produced.

2. A process for the production of an 8,13-dimethyl polyhydrophenanthrene 8-tertiary carbinol having as a Z-substituent an a-carbonylated aliphatic radical selected from the group consisting of --COCH and COOH, from a corresponding 8,13-dimethyl polyhydrophenanthrene 8-tertiary carbinol reactant compound having as a Z-substituent an aliphatic radical selected from the group consisting of -CH(CH CH=CH CHOHCH and CHOHCH OH, the nucleus of which reactant is resistant to rupture by oxidation under the process conditions and the l3-angular methyl and S-tertiary carbinol groups are in trans relationship, which process comprises subjecting said carbinol reactant compound to the action of a hexavalent chromium compound under oxidizing 10 conditions, whereby said tertiary carbinol having said Z-a-carbonylated substituent-is produced. I

3. A process of claim 1, wherein the reactant compound is added to a mixture of a' hexavalent chromium compound and an orthophosphate producing compound and the resulting mixture is subjected to a temperature in the range of 5 to below about 7 0 C.

1 4. A'process of claim 3, wherein a product having an aceto group as a 2-substituent is produced.

5. A process of claim 1, wherein the 2-substituent is a carboxyl group, followed by subjecting the product to the action of a hydroxyl containing hydrocarbon esteri fication agent, said agent being a member of the group of alkyl and aryl monohydric alcohols, whereby a corresponding product havinga Z-carboxylic ester substituent is produced.

6. A process of claim 3, wherein the nucleus contains at least one and at most two halogens.

7. A process of claim 6, wherein. a carbinol having an aceto group as a 2-substituent is produced.

8. A process of claim 6, followed by subjecting the product to the action of a halogen removing agent whereby a product having at least one and at most four nuclear double bonds is produced.

9. A process of claim 8, wherein a carbinol havingone nuclear double bond in the 1:2 position is produced.

10. A process of claim 2, wherein the tertiary carbinol is a diphenyl carbinol.

11. A process of claim 6, 1,2-dibromo substituted. Y

12. Ap'rocess of claim 8, wherein a carbinol having one nuclear double bond in the 1:2 position is produced from a 1,2-dibromo carbinol.

13. An 8,13-dimethyl polyhydrophenanthrene-8-tertiary carbinol having as a Z-substitu'en't an u-carbonylated radical selected from the groupconsisting of COCH and --COOR (wherein R is a member of the group consisting of hydrogen, alkyl and aryl radicals) wherein the Ill-angular methyl and 8-tertiary carbinol groups are in transrelationship and the phenanthrene nucleus'contains at most'four double bonds, said double bonds are located in rings B and C of the structural skeleton wherein the nucleus is wherein y represents the said 8-tertiary carbinol group and x represents the said Z-substituent group.

14. A carbinol of claim 13, wherein the phenanthrene A Y B mo OOH P Ph wherein Ph is phenyl.

'20. A carbinol having a formula wherein Ph is phenyl.

21 A carbinol having aformula wherein Ph is phenyl.

22. A carbinol having aformula sisting pf hydrogemqalkiyl and aryl radicals) wherein the Iii-angular methyl and" said a8-tert iarily .bonded ez-carhonylated substituents are in trans relationship, and the phenanthrene nucleus having at most four double bonds,

said double bonds being located in the B and C rings of the structural skeleton H20 2 wherein z represents" the, said tertiarily bonded 8-a,-.carbonylated substituent and x represents the said Z-a-carbonylated substituent.

24. A compound of claim 23, having an aceto group as the Z-sUbStituent.

25. A compound having a formula i i i CH3 C O 0 CH3 HzC H36 COOCH:

References Cited in the file of this patent UNITED STATES PATENTS 2,323,584 Schoeller et a1. July 6, 1943 2,703,809 Ritchie Mar. 8, 1955 2,744,101 Subluskey F 2. May 1 1956 OTHER REFERENCES Zeiss: J. Am. Chem. Soc, vol. 70, pp. 858436011948). Fieser et al.: Natural Products Related to 'Phenanthrene, pp. 61-63 (1949). f

Merck Index, 6th ed. (1952), page 760.

Sanderson u June/12,1956 

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